US4053505A - Preparation of n-phosphonomethyl glycine - Google Patents

Preparation of n-phosphonomethyl glycine Download PDF

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US4053505A
US4053505A US05/646,724 US64672476A US4053505A US 4053505 A US4053505 A US 4053505A US 64672476 A US64672476 A US 64672476A US 4053505 A US4053505 A US 4053505A
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phosphonomethyl glycine
reaction
triester
phosphonomethyl
glycine
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US05/646,724
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Gerard A. Dutra
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Monsanto Co
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Monsanto Co
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Priority to US05/646,724 priority Critical patent/US4053505A/en
Priority to EG736/76A priority patent/EG12660A/en
Priority to JP15762776A priority patent/JPS5285122A/en
Priority to ES454709A priority patent/ES454709A1/en
Priority to NLAANVRAGE7614584,A priority patent/NL183033C/en
Priority to YU3201/76A priority patent/YU39981B/en
Priority to BR7700009A priority patent/BR7700009A/en
Priority to SU772434855A priority patent/SU662015A3/en
Priority to IL51203A priority patent/IL51203A/en
Priority to BE173813A priority patent/BE850059A/en
Priority to FR7700026A priority patent/FR2337143A1/en
Priority to PL1977195088A priority patent/PL105557B1/en
Priority to ZA770009A priority patent/ZA779B/en
Priority to MX775277U priority patent/MX4089E/en
Priority to SE7700032A priority patent/SE7700032L/en
Priority to HU77MO972A priority patent/HU174617B/en
Priority to AR266093A priority patent/AR224493A1/en
Priority to DK377A priority patent/DK377A/en
Priority to IT19005/77A priority patent/IT1075476B/en
Priority to AT277A priority patent/AT348544B/en
Priority to RO7788924A priority patent/RO71661A/en
Priority to PH19311A priority patent/PH13277A/en
Priority to DD7700196793A priority patent/DD129103A5/en
Priority to CS7739A priority patent/CS193080B2/en
Priority to DE2700017A priority patent/DE2700017C2/en
Priority to CH577A priority patent/CH623595A5/de
Priority to AU21027/77A priority patent/AU508058B2/en
Priority to IE12/77A priority patent/IE44245B1/en
Priority to GB124/77A priority patent/GB1527191A/en
Application granted granted Critical
Publication of US4053505A publication Critical patent/US4053505A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof

Definitions

  • This invention relates to a process for the production of N-phosphonomethyl glycine, which compound is useful as a post-emergent herbicide.
  • a process for producing N-phosphonomethyl glycine comprises (a) reacting a dihydrocarbon phosphite with 1,3,5-tricarboalkoxymethylhexahydro-1,3,5-triazine to form a triester of N-phosphonomethyl glycine; (b) hydrolyzing the triester and recovering the N-phosphonomethyl glycine.
  • R and R' are monovalent hydrocarbon group or substituted monovalent hydrocarbon groups, the substituents being those which are inert to the reaction.
  • the process is carried out by forming an admixture of the hexahydrotriazine and the phosphite ester and heating the admixture to a temperature sufficiently elevated to initiate the reaction of the phosphite ester with the hexahydrotriazine and thereafter maintaining the admixture at a temperature sufficient to maintain said reaction until said reaction is essentially complete.
  • the R and R' groups do not enter into the initial reaction between the triazine and the phosphite, therefore the nature of these groups is not critical. These groups are removed when the triester of N-phosphonomethyl glycine is subjected to hydrolysis.
  • the R group is an aliphatic radical and the R' group are monocyclic aryl hydrocarbon radicals, substituted aryl radicals, benzyl radicals, substituted benzyl radicals or aliphatic radicals containing from 1 to 6 carbon atoms.
  • the R groups are lower alkyl radicals containing from 1 to 4 carbon atoms and the R' groups are phenyl, benzyl or lower alkyl radicals.
  • step (a) of the process no catalyst is required.
  • the reaction goes essentially to completion by merely heating the reactants to a temperature of from 20° C. to 150° C.
  • a catalyst such as a Lewis acid can be employed but no commensurate advantages are obtained thereby.
  • the temperature at which step (a) of the process is conducted can vary over wide ranges.
  • the temperature employed should be one which is sufficiently elevated so as to initiate and maintain the reaction. Temperatures in the range of from 20° C. to 150° C. are generally preferred. Temperatures in the range of from 30° C. to 120° C. are particularly preferred.
  • the process of this invention can be conducted at atmospheric pressure, sub-atmospheric pressure or super-atmospheric pressure. For convenience and economy, it is preferred to conduct the process of this invention at atmospheric pressure.
  • a solvent is sometimes desirable where one or more of the reactants is a solid and also in order to more readily control the temperature of the reaction by conducting the reaction at the boiling point of the solvent employed.
  • the solvents which can be employed in the reaction of the hexahydrotriazine with the phosphite ester are those solvents in which the triazine and the phosphite are soluble and which are themselves inert to reaction with the hexahydrotriazine or phosphite ester.
  • solvents are for example acetonitrile, benzene, toluene, xylene, mono- and di-chloro-benzene, methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, dimethylformamide, tetrahydrofurane, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethylether, and the like.
  • a ratio of the triazine to phosphite ester is not critical.
  • the molar ratio of phosphite to triazine should be 3 to 1 in order to obtain the best yield. Ratios of from 1 to 10 to 10 to 1 could be employed, however, ratios outside approximately 3 to 1 are unnecessarily wasteful of reagents and may render it more difficult to recover the desired product.
  • step (a) of the process of this invention After conducting step (a) of the process of this invention to produce the triester, one can distill off the solvent, if a solvent is employed, before or after the addition of the hydrolysis medium, i.e., the hydrohalic acid or base solution.
  • the hydrolysis medium i.e., the hydrohalic acid or base solution.
  • the second step (b) of the process of this invention is preferably carried out by refluxing the triester with an aqueous mineral acid such as sulfuric, hydrochloric or hydrobromic acid which is at least 1.0 normal.
  • an aqueous mineral acid such as sulfuric, hydrochloric or hydrobromic acid which is at least 1.0 normal.
  • the hydrochloric acid or hydrobromic acids are preferred since being volatile they are easily removed from the reaction mixture by concentrating the mixture. The concentrated mixture is then cooled to precipitate the N-phosphonomethyl glycine.
  • the second step (b) of the process of this invention can also be carried out by heating the triester with a caustic solution of an alkali metal or alkaline earth metal hydroxide in a water, or aliphatic alcohol solution or mixtures of such solvents. Inasmuch as a salt would be produced it is necessary to acidify such salts in order to recover the free acid if the free acid is the desired product.
  • aqueous hydrohalic acid be at least 1.0 normal and even more preferred that it be 2.0 normal.
  • concentrated aqueous hydrohalic acids can be employed, but no commensurate advantages are obtained thereby.
  • any of the alkali or alkaline earth metal hydroxides can be employed, the alkali metal hydroxide of lithium, potassium, sodium, rubidium or cesium being preferred, sodium and potassium hydroxides being especially preferred. It is preferred to employ these hydroxides in aqueous solution and at least 0.05 normal. It is of course apparent from the above equation that for best results at least three moles of the alkali metal hydroxide should be employed for each mole of the triester. It is especially preferred to employ about six moles of the alkali metal hydroxide for each mole of the triester of N-phosphonomethyl glycine.
  • the hydrolysis step (b) of this invention is preferably conducted at temperatures of from 70° to 150° C. or even higher. It is especially preferred that the temperature employed be from 85° C. to about 125° C. for economy and ease of reaction.
  • the monovalent hydrocarbon radical represented by R and R' are for example lower aliphatic groups such as alkyl, alkenyl and alkynyl groups containing from 1 to 6 carbon atoms and such group substituted with a substituent which is inert to the reaction.
  • Such lower aliphatic groups are methyl, ethyl, propyl, butyl, hexyl, vinyl, allyl, butenyl, butynyl, ethynyl, propynyl, hexynyl and the like, benzyl, phenethyl and the like.
  • R and R' can also be phenyl or naphthyl and such groups substituted with substituents which are inert to the reaction.
  • inert groups include lower alkyl, lower alkoxy, lower alkylthio, trifluoromethyl, carbo lower alkoxy, nitro, halo, e.g. chloro, bromo, fluoro or iodo, phenyl, benzyloxy and the like.
  • 1,3,5-tricarbohydrocarbonoxymethyl hexahydrotriazines employed in the process of this invention are produced by the reaction of formaldehyde with a hydrocarbon ester of glycine.
  • phosphite esters employed in the process of this invention are readily available from commercial sources or can be readily produced by the reaction of a hydrocarbon alcohol with phosphorus trichloride by known methods.
  • N-phosphonomethyl glycine produced is useful as a post-emergent contact herbicide particularly against perennial plant species.
  • 1,3,5-Tricarbethoxymethylhexahydro-1,3,5-triazine (1.38 parts),di-(4-methoxyphenyl)phosphite (3.53 parts containing 0.15 parts of 4 -methoxyphenol) and dry benzene (50 ml) were mixed and heated to reflux for 2 hours, and then allowed to stand overnight.
  • Nuclear magnetic resonance spectral analysis indicated that a complete conversion to the ethyl N-[di(4-methoxyphenoxy)-phosphonomethyl]glycinate was obtained.
  • the reaction mixture was concentrated under vacuum, diluted with 2 normal hydrochloric acid (225 ml) and heated to reflux for 2 hours.
  • This reaction mixture was concentrated and then mixed with a mixture of water and methylene chloride. The water layer was then extracted four times with methylene chloride. The aqueous layer was concentrated to yield 1.46 parts of a white solid identified as N-phosphonomethyl glycine and which when mixed with an authentic sample of N-phosphonomethyl glycine showed no differences in a nuclear magnetic resonance spectral analysis.
  • 1,3,5-Tricarbethoxymethylhexahydro-1,3,5-triazine (1.38 parts) and diphenyl phosphite (2.81 parts) are dissolved in benzene and heated to reflux for 2 hours, and then allowed to stand for 16 hours at ambient temperatures.
  • the reaction mixture is concentrated under vacuum and an excess of dilute sodium hydroxide added and then heated to from 70° C. to 100° C for 6 hours.
  • the resultant solution was then neutralized with hydrochloric acid, then allowed to stand at ambient temperature to precipitate the N-phosphonomethyl glycine. By this procedure one obtains substantially theoretical yields of the N-phosphonomethyl glycine.
  • Di(4-chlorobenzyl)phosphite (2 parts) was mixed with N-methylene ethyl glycinate trimer (0.69 parts) in dry benzene ( ⁇ 150 parts) and heated to reflux for 20 hours.
  • the benzene was distilled off and the residue diluted with two normal hydrochloric acid (125 parts) and heated to reflux temperature ( ⁇ 100° C.) for 22.5 hours.
  • the reaction mixture was concentrated to dryness, dissolved in water and extracted with methylene chloride.
  • the water solution was concentrated to a small volume and allowed to stand to precipitate a white solid.
  • the white solid was identified as N-phosphonomethyl glycine by mixing it with an authentic sample and conducting nuclear magnetic resonance spectral analysis. The total isolated yield was 63% of theoretical.
  • 1,3,5-Tricarbethoxymethylhexahydro-1,3,5-triazine (5.76 parts) and di(4-methoxyphenyl)phosphite (15.3 parts containing 0.6 parts of 4-methoxyphenol) were mixed and heated to 80° C. for from 1/2 to 1 hour.
  • Nuclear magnetic resonance spectral analysis indicated that a complete conversion to the ethyl N-[di(4-methoxyphenoxy)-phosphonomethyl]glycinate was obtained.
  • the reaction mixture can then be diluted with 2 normal hydrochloric acid (225 ml) and heated to reflux for 2 hours. This reaction mixture is concentrated and then mixed with a mixture of water and methylene chloride. The water layer is then extracted with methylene chloride. The aqueous layer is concentrated to yield N-phosphonomethyl glycine.
  • Diethyl phosphite (1.38 parts) and 1,3,5-tricarbethoxymethylhexahydro-1,3,5-triazine (1.15 parts) were mixed in a pyrex glass reaction vessel and heated to 100° C. for 3 hours.
  • the glycinate is then diluted with concentrated hydrochloric acid and heated to about 100° C. for 6 hours and then concentrated to dryness.
  • the N-phosphonomethylglycine is dissolved in a small amount of hot water and then allowed to cool to precipitate essentially pure N-phosphonomethyl glycine.

Abstract

A herbicidal compound N-phosphonomethyl glycine is prepared by (a) reacting 1,3,5-tricarbohydrocarbonoxymethyl hexahydrotriazine with a di-monovalent hydrocarbon phosphite to form an ester of N-phosphonomethyl glycine which is thereafter (b) hydrolyzed and the N-phosphonomethyl glycine is recovered.

Description

This invention relates to a process for the production of N-phosphonomethyl glycine, which compound is useful as a post-emergent herbicide.
In accordance with the present invention, there is provided a process for producing N-phosphonomethyl glycine, which process comprises (a) reacting a dihydrocarbon phosphite with 1,3,5-tricarboalkoxymethylhexahydro-1,3,5-triazine to form a triester of N-phosphonomethyl glycine; (b) hydrolyzing the triester and recovering the N-phosphonomethyl glycine.
The following equation illustrates the reaction: ##STR1## wherein R and R' are monovalent hydrocarbon group or substituted monovalent hydrocarbon groups, the substituents being those which are inert to the reaction. In accordance with the present invention the process is carried out by forming an admixture of the hexahydrotriazine and the phosphite ester and heating the admixture to a temperature sufficiently elevated to initiate the reaction of the phosphite ester with the hexahydrotriazine and thereafter maintaining the admixture at a temperature sufficient to maintain said reaction until said reaction is essentially complete.
In the above reaction the R and R' groups do not enter into the initial reaction between the triazine and the phosphite, therefore the nature of these groups is not critical. These groups are removed when the triester of N-phosphonomethyl glycine is subjected to hydrolysis. Conveniently the R group is an aliphatic radical and the R' group are monocyclic aryl hydrocarbon radicals, substituted aryl radicals, benzyl radicals, substituted benzyl radicals or aliphatic radicals containing from 1 to 6 carbon atoms. Preferably the R groups are lower alkyl radicals containing from 1 to 4 carbon atoms and the R' groups are phenyl, benzyl or lower alkyl radicals.
In step (a) of the process no catalyst is required. The reaction goes essentially to completion by merely heating the reactants to a temperature of from 20° C. to 150° C. A catalyst such as a Lewis acid can be employed but no commensurate advantages are obtained thereby.
The temperature at which step (a) of the process is conducted can vary over wide ranges. The temperature employed should be one which is sufficiently elevated so as to initiate and maintain the reaction. Temperatures in the range of from 20° C. to 150° C. are generally preferred. Temperatures in the range of from 30° C. to 120° C. are particularly preferred.
The process of this invention can be conducted at atmospheric pressure, sub-atmospheric pressure or super-atmospheric pressure. For convenience and economy, it is preferred to conduct the process of this invention at atmospheric pressure.
Although a solvent is not necessary in conducting the process of this invention, a solvent is sometimes desirable where one or more of the reactants is a solid and also in order to more readily control the temperature of the reaction by conducting the reaction at the boiling point of the solvent employed. The solvents which can be employed in the reaction of the hexahydrotriazine with the phosphite ester are those solvents in which the triazine and the phosphite are soluble and which are themselves inert to reaction with the hexahydrotriazine or phosphite ester. These solvents are for example acetonitrile, benzene, toluene, xylene, mono- and di-chloro-benzene, methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, dimethylformamide, tetrahydrofurane, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethylether, and the like.
In step (a) of the process of this invention a ratio of the triazine to phosphite ester is not critical. As can be seen from the above equation, the molar ratio of phosphite to triazine should be 3 to 1 in order to obtain the best yield. Ratios of from 1 to 10 to 10 to 1 could be employed, however, ratios outside approximately 3 to 1 are unnecessarily wasteful of reagents and may render it more difficult to recover the desired product.
After conducting step (a) of the process of this invention to produce the triester, one can distill off the solvent, if a solvent is employed, before or after the addition of the hydrolysis medium, i.e., the hydrohalic acid or base solution.
The second step (b) of the process of this invention is preferably carried out by refluxing the triester with an aqueous mineral acid such as sulfuric, hydrochloric or hydrobromic acid which is at least 1.0 normal. The hydrochloric acid or hydrobromic acids are preferred since being volatile they are easily removed from the reaction mixture by concentrating the mixture. The concentrated mixture is then cooled to precipitate the N-phosphonomethyl glycine.
The second step (b) of the process of this invention can also be carried out by heating the triester with a caustic solution of an alkali metal or alkaline earth metal hydroxide in a water, or aliphatic alcohol solution or mixtures of such solvents. Inasmuch as a salt would be produced it is necessary to acidify such salts in order to recover the free acid if the free acid is the desired product.
In conducting the hydrolysis step (b) of this invention employing aqueous hydrochloric or hydrobromic acid, it is preferred that the aqueous hydrohalic acid be at least 1.0 normal and even more preferred that it be 2.0 normal. Of course, concentrated aqueous hydrohalic acids can be employed, but no commensurate advantages are obtained thereby.
Where a basic solution is employed to hydrolyze the triester, any of the alkali or alkaline earth metal hydroxides can be employed, the alkali metal hydroxide of lithium, potassium, sodium, rubidium or cesium being preferred, sodium and potassium hydroxides being especially preferred. It is preferred to employ these hydroxides in aqueous solution and at least 0.05 normal. It is of course apparent from the above equation that for best results at least three moles of the alkali metal hydroxide should be employed for each mole of the triester. It is especially preferred to employ about six moles of the alkali metal hydroxide for each mole of the triester of N-phosphonomethyl glycine.
The hydrolysis step (b) of this invention is preferably conducted at temperatures of from 70° to 150° C. or even higher. It is especially preferred that the temperature employed be from 85° C. to about 125° C. for economy and ease of reaction.
The monovalent hydrocarbon radical represented by R and R' are for example lower aliphatic groups such as alkyl, alkenyl and alkynyl groups containing from 1 to 6 carbon atoms and such group substituted with a substituent which is inert to the reaction. Such lower aliphatic groups are methyl, ethyl, propyl, butyl, hexyl, vinyl, allyl, butenyl, butynyl, ethynyl, propynyl, hexynyl and the like, benzyl, phenethyl and the like. R and R' can also be phenyl or naphthyl and such groups substituted with substituents which are inert to the reaction. Illustrative of such inert groups but not limiting are the following groups: lower alkyl, lower alkoxy, lower alkylthio, trifluoromethyl, carbo lower alkoxy, nitro, halo, e.g. chloro, bromo, fluoro or iodo, phenyl, benzyloxy and the like.
The 1,3,5-tricarbohydrocarbonoxymethyl hexahydrotriazines employed in the process of this invention are produced by the reaction of formaldehyde with a hydrocarbon ester of glycine.
The phosphite esters employed in the process of this invention are readily available from commercial sources or can be readily produced by the reaction of a hydrocarbon alcohol with phosphorus trichloride by known methods.
The N-phosphonomethyl glycine produced is useful as a post-emergent contact herbicide particularly against perennial plant species.
The following examples serve to further illustrate this invention. All parts are parts by weight unless otherwise specifically set forth.
EXAMPLE 1
1,3,5-Tricarbethoxymethylhexahydro-1,3,5-triazine (1.38 parts),di-(4-methoxyphenyl)phosphite (3.53 parts containing 0.15 parts of 4 -methoxyphenol) and dry benzene (50 ml) were mixed and heated to reflux for 2 hours, and then allowed to stand overnight. Nuclear magnetic resonance spectral analysis indicated that a complete conversion to the ethyl N-[di(4-methoxyphenoxy)-phosphonomethyl]glycinate was obtained. The reaction mixture was concentrated under vacuum, diluted with 2 normal hydrochloric acid (225 ml) and heated to reflux for 2 hours. This reaction mixture was concentrated and then mixed with a mixture of water and methylene chloride. The water layer was then extracted four times with methylene chloride. The aqueous layer was concentrated to yield 1.46 parts of a white solid identified as N-phosphonomethyl glycine and which when mixed with an authentic sample of N-phosphonomethyl glycine showed no differences in a nuclear magnetic resonance spectral analysis.
Workup of the methylene chloride solution with water yielded an additional 0.22 parts of N-phosphonomethyl glycine: total yield 83% of theory.
EXAMPLE 2
1,3,5-Tricarbethoxymethylhexahydro-1,3,5-triazine (1.38 parts) and diphenyl phosphite (2.81 parts) are dissolved in benzene and heated to reflux for 2 hours, and then allowed to stand for 16 hours at ambient temperatures. The reaction mixture is concentrated under vacuum and an excess of dilute sodium hydroxide added and then heated to from 70° C. to 100° C for 6 hours. The resultant solution was then neutralized with hydrochloric acid, then allowed to stand at ambient temperature to precipitate the N-phosphonomethyl glycine. By this procedure one obtains substantially theoretical yields of the N-phosphonomethyl glycine.
EXAMPLE 3
Di(4-chlorobenzyl)phosphite (2 parts) was mixed with N-methylene ethyl glycinate trimer (0.69 parts) in dry benzene (˜150 parts) and heated to reflux for 20 hours. The benzene was distilled off and the residue diluted with two normal hydrochloric acid (125 parts) and heated to reflux temperature (˜100° C.) for 22.5 hours. The reaction mixture was concentrated to dryness, dissolved in water and extracted with methylene chloride. The water solution was concentrated to a small volume and allowed to stand to precipitate a white solid. The white solid was identified as N-phosphonomethyl glycine by mixing it with an authentic sample and conducting nuclear magnetic resonance spectral analysis. The total isolated yield was 63% of theoretical.
EXAMPLE 4
1,3,5-Tricarbethoxymethylhexahydro-1,3,5-triazine (5.76 parts) and di(4-methoxyphenyl)phosphite (15.3 parts containing 0.6 parts of 4-methoxyphenol) were mixed and heated to 80° C. for from 1/2 to 1 hour. Nuclear magnetic resonance spectral analysis indicated that a complete conversion to the ethyl N-[di(4-methoxyphenoxy)-phosphonomethyl]glycinate was obtained. The reaction mixture can then be diluted with 2 normal hydrochloric acid (225 ml) and heated to reflux for 2 hours. This reaction mixture is concentrated and then mixed with a mixture of water and methylene chloride. The water layer is then extracted with methylene chloride. The aqueous layer is concentrated to yield N-phosphonomethyl glycine.
EXAMPLE 5
1,3,5-Tricarbomethoxymethylhexahydro-1,3,5-triazine (1.0 part) and diphenyl phosphite (2.93 parts which contained .59 parts of phenol) are mixed and then heated to 80° C. for 5 minutes. To the reaction mixture is then added an excess of dilute hydrochloric acid (2.0 N) and then heated to from 70° C. to 100° C. for 6 hours. The resultant solution is then allowed to stand at ambient temperature to precipitate the N-phosphonomethyl glycine. By this procedure one obtains yields of the N-phosphonomethyl glycine of greater than 80%.
EXAMPLE 6
Diethyl phosphite (1.38 parts) and 1,3,5-tricarbethoxymethylhexahydro-1,3,5-triazine (1.15 parts) were mixed in a pyrex glass reaction vessel and heated to 100° C. for 3 hours. Nuclear magnetic resonance spectral analysis indicated that a complete conversion to ethyl N-(diethoxyphoephonomethyl)-glycinate (nD /25 1.4468). The glycinate is then diluted with concentrated hydrochloric acid and heated to about 100° C. for 6 hours and then concentrated to dryness. The N-phosphonomethylglycine is dissolved in a small amount of hot water and then allowed to cool to precipitate essentially pure N-phosphonomethyl glycine.
When hydrobromic acid is employed in the above procedure the same results are obtained.
Although the invention is described with respect to specific modifications, the details thereof are not to be construed as limitations except to the extent indicated in the following claims.

Claims (7)

What is claimed is:
1. A process for the production of N-phosphonomethyl glycine which comprises (a) reacting a 1,3,5-tricarbohydrocarbonoxy-methyl-hexahydrotriazine of the formula ##STR2## wherein R is a monovalent hydrocarbon or substituted hydrocarbon radical in which the substituent is inert to the reaction; with a phosphite ester of the formula ##STR3## wherein the R' is the same or different radical as defined for R, in the absence of a catalyst, by heating a mixture of said triazine and said ester to a temperature sufficiently elevated to initiate and maintain the reaction to form a triester of N-phosphonomethyl glycine of the formula ##STR4## wherein R and R' are as above defined, (b) hydrolyzing the triester and (c) recovering N-phosphonomethyl glycine.
2. A process of claim 1 wherein step (a) is conducted in the presence of a suitable solvent.
3. A process according to claim 2 wherein said triester of N-phosphonomethyl glycine is isolated before the hydrolysis by removing the solvent.
4. A process according to claim 1 wherein R represents an alkyl radical of from 1 to 6 carbon atoms and R' represents a phenyl or substituted phenyl radical.
5. A process in accordance with claim 1 wherein the temperature is between 20° C. and 150° C.
6. A process in accordance with claim 1 wherein the hydrolysis is carried out in aqueous hydrohalic acid having a normality of at least 1.0.
7. A process according to claim 2 wherein aqueous hydrohalic acid is added to the reaction mixture before the removal of the solvent.
US05/646,724 1976-01-05 1976-01-05 Preparation of n-phosphonomethyl glycine Expired - Lifetime US4053505A (en)

Priority Applications (29)

Application Number Priority Date Filing Date Title
US05/646,724 US4053505A (en) 1976-01-05 1976-01-05 Preparation of n-phosphonomethyl glycine
EG736/76A EG12660A (en) 1976-01-05 1976-11-27 Process for preparation of n-phosphonomephyl glycine used as herbicides
JP15762776A JPS5285122A (en) 1976-01-05 1976-12-28 Process for manufacturing nnphosphonomethylglycin
ES454709A ES454709A1 (en) 1976-01-05 1976-12-30 Preparation of n-phosphonomethyl glycine
NLAANVRAGE7614584,A NL183033C (en) 1976-01-05 1976-12-30 PROCESS FOR THE PREPARATION OF N-PHOSPHONOMETHYLGLYCIN.
YU3201/76A YU39981B (en) 1976-01-05 1976-12-31 Process for obtaining n-phosphono-methylglycine
AT277A AT348544B (en) 1976-01-05 1977-01-03 METHOD FOR PRODUCING N-PHOSPHONOMETHYLGLYCINE
IL51203A IL51203A (en) 1976-01-05 1977-01-03 Preparation of n-phosphonomethyl glycine
BE173813A BE850059A (en) 1976-01-05 1977-01-03 PROCESS FOR PREPARING N-PHOSPHONOMETHYLGLYCINE AND NEW PRODUCT THUS OBTAINED
FR7700026A FR2337143A1 (en) 1976-01-05 1977-01-03 PROCESS FOR PREPARING N-PHOSPHONOMETHYLGLYCINE AND NEW PRODUCT THUS OBTAINED
PL1977195088A PL105557B1 (en) 1976-01-05 1977-01-03 METHOD OF PRODUCING N-PHOSPHONOMETHYLGLICINE
ZA770009A ZA779B (en) 1976-01-05 1977-01-03 Preparation of n-phosphonomethyl glycine
MX775277U MX4089E (en) 1976-01-05 1977-01-03 IMPROVED PROCEDURE FOR THE PREPARATION OF N-PHOSPHONOMETILGLICINA
SE7700032A SE7700032L (en) 1976-01-05 1977-01-03 PREPARATION OF N-PHOSPHONOMETHYLGLYSIN
BR7700009A BR7700009A (en) 1976-01-05 1977-01-03 PROCESS FOR THE PRODUCTION OF N-PHOSPHONOMETHYL-GLYCINE
AR266093A AR224493A1 (en) 1976-01-05 1977-01-03 A PROCEDURE FOR THE PRODUCTION OF N-PHOSPHONOMETYL GLYCINE
DK377A DK377A (en) 1976-01-05 1977-01-03 PROCEDURE FOR THE PREPARATION OF N-PHOSPHONOMETHYL-GLYCIN
IT19005/77A IT1075476B (en) 1976-01-05 1977-01-03 PREPARATION OF N-FOSFON-METHYL-GLYCINE
SU772434855A SU662015A3 (en) 1976-01-05 1977-01-03 Method of obtaining n-phosphonomethylglycine
RO7788924A RO71661A (en) 1976-01-05 1977-01-03 PROCESS FOR OBTAINING N-PHOSPHONOMETHYLGLYCIN
PH19311A PH13277A (en) 1976-01-05 1977-01-03 Preparation of n-phosphonomethyl glycine
DD7700196793A DD129103A5 (en) 1976-01-05 1977-01-03 PROCESS FOR PREPARING N-PHOSPHONOMETHYLGLYCIN
CS7739A CS193080B2 (en) 1976-01-05 1977-01-03 Process for preparing n-phosphonomethylglycine
DE2700017A DE2700017C2 (en) 1976-01-05 1977-01-03 Process for the production of N-phosphonomethylglycine
CH577A CH623595A5 (en) 1976-01-05 1977-01-03
HU77MO972A HU174617B (en) 1976-01-05 1977-01-03 Process for producing n-phosphonomethylglycine
AU21027/77A AU508058B2 (en) 1976-01-05 1977-01-04 Preparation of n-phosphonomethyl glycine
IE12/77A IE44245B1 (en) 1976-01-05 1977-01-04 A process for the production of n-phosphonomethyl glycine
GB124/77A GB1527191A (en) 1976-01-05 1977-01-05 Process for the production of n-phosphonomethyl glycine

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180394A (en) * 1978-07-10 1979-12-25 Monsanto Company Derivatives of N-trifluoroacetyl-N-phosphonomethylglycinates and the herbicidal use thereof
US4218235A (en) * 1978-07-10 1980-08-19 Monsanto Company Ester derivatives of n-trifluoroacetyl-n-phosphonomethylglycine and the herbicidal use thereof
US4251258A (en) * 1978-09-29 1981-02-17 Monsanto Company N-(Substituted carbonyl) derivatives of N-phosphinylmethylglycinates and the herbicidal use thereof
US4300942A (en) * 1978-09-29 1981-11-17 Monsanto Company N-(Substituted carbonyl) derivatives of N-phos-phinylmethylglycinates and the herbicidal use thereof
US4368162A (en) * 1981-11-02 1983-01-11 Ciba-Geigy Corporation Process for producing aminomethylphosphonic acid
US4389349A (en) * 1982-01-25 1983-06-21 Cho Hung H Process for preparing of N-phosphenomethyl glycine
US4415503A (en) * 1982-09-28 1983-11-15 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
US4422982A (en) * 1982-06-30 1983-12-27 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
EP0102694A1 (en) * 1982-07-29 1984-03-14 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
EP0104775A1 (en) * 1982-08-30 1984-04-04 Stauffer Chemical Company Production of N-phosphonomethylglycine
US4487724A (en) * 1982-08-23 1984-12-11 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
EP0149294A1 (en) * 1982-08-16 1985-07-24 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
US4634788A (en) * 1985-06-06 1987-01-06 Monsanto Company Herbicidal glyphosate oxime derivatives
EP0374410A2 (en) * 1988-11-23 1990-06-27 American Cyanamid Company 2-Azabicyclo[2.2.1]hept-5-ene-2-acetic acid, derivatives thereof and related compounds, process for the preparation of said compounds and the use of said compounds for the manufacture of N-phosphonomethylglycine
US5053529A (en) * 1990-05-25 1991-10-01 Korea Institute Of Science And Technology Process for the preparation of N-phosphonomethylglycine
US5120871A (en) * 1991-05-16 1992-06-09 American Cyanamid Company N-[(pentaalkyl-cyclopentadienyl)methyl]-glycines, process for the preparation of the compounds and the use thereof in the manufacture of N-phosphonomethylglycine
US5149825A (en) * 1988-11-23 1992-09-22 American Cyanamid Company 2-azabicyclo(2.2.1)hept-5-ene-2-acetic acid, derivatives thereof and related compounds, process for the preparation of said compounds and the use of said compounds for the manufacture of N-phosphonomethylglycine
US5155100A (en) * 1991-05-01 1992-10-13 Ciba-Geigy Corporation Phosphono/biaryl substituted dipeptide derivatives
US5210277A (en) * 1991-05-16 1993-05-11 American Cyanamid Company N-[pentaalkyl-cyclopentadienyl)methyl]-glycines
US5270473A (en) * 1991-05-16 1993-12-14 American Cyanamid Company N-[(pentaalkyl-cyclopentadienyl)methyl]-glycines, process for the preparation of the compounds and the use thereof in the manufacture of N-phosphonomethylglycine
US5294632A (en) * 1991-05-01 1994-03-15 Ciba-Geigy Corporation Phosphono/biaryl substituted dipetide derivatives
US20030004370A1 (en) * 1999-12-23 2003-01-02 Christian Wulff Method for production of n-phosphonomethylglycine
US20040236145A1 (en) * 2001-06-22 2004-11-25 Christian Wulff Method for producing n-phosphonomethylglycine

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2829046A1 (en) * 1978-07-01 1980-01-10 Benckiser Knapsack Gmbh METHOD FOR PRODUCING ACYLAMINO METHANPHOSPHONIC ACIDS
CH647528A5 (en) * 1978-10-27 1985-01-31 Bcap Biolog Chem Act Pat PROCESS FOR THE PREPARATION OF N-phosphonomethylglycine.
HU184601B (en) * 1979-07-09 1984-09-28 Alkaloida Vegyeszeti Gyar Process for producing n-/phosphono-methyl/-glycine
DE10130134A1 (en) * 2001-06-22 2003-01-02 Basf Ag Process for the preparation of alpha-aminophosphonic acids

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288846A (en) * 1961-11-13 1966-11-29 Monsanto Co Processes for preparing organophosphonic acids
US3476799A (en) * 1965-12-16 1969-11-04 Knapsack Ag Process for the manufacture of nitrilo-tris-methylene phosphonic acid
US3549728A (en) * 1966-02-14 1970-12-22 Ugine Kuhlmann Phosphorus and nitrogen-containing polyols
US3799758A (en) * 1971-08-09 1974-03-26 Monsanto Co N-phosphonomethyl-glycine phytotoxicant compositions
US3886204A (en) * 1970-12-16 1975-05-27 Bayer Ag 2-Phosphono-butane-1,2,3,4-tetracarboxylic acids
US3923877A (en) * 1972-11-08 1975-12-02 Ici Ltd Preparation of N-phosphonomethyl glycine

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX3898E (en) * 1975-12-29 1981-09-10 Monsanto Co IMPROVED PROCEDURE FOR THE PREPARATION OF N-PHOSPHONOMETILGLYCLE TRIESTERS

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3288846A (en) * 1961-11-13 1966-11-29 Monsanto Co Processes for preparing organophosphonic acids
US3476799A (en) * 1965-12-16 1969-11-04 Knapsack Ag Process for the manufacture of nitrilo-tris-methylene phosphonic acid
US3549728A (en) * 1966-02-14 1970-12-22 Ugine Kuhlmann Phosphorus and nitrogen-containing polyols
US3886204A (en) * 1970-12-16 1975-05-27 Bayer Ag 2-Phosphono-butane-1,2,3,4-tetracarboxylic acids
US3799758A (en) * 1971-08-09 1974-03-26 Monsanto Co N-phosphonomethyl-glycine phytotoxicant compositions
US3923877A (en) * 1972-11-08 1975-12-02 Ici Ltd Preparation of N-phosphonomethyl glycine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Adams et al., "Organic Synthesis" Collective vol. 1, pp. 355-357. *

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4218235A (en) * 1978-07-10 1980-08-19 Monsanto Company Ester derivatives of n-trifluoroacetyl-n-phosphonomethylglycine and the herbicidal use thereof
US4180394A (en) * 1978-07-10 1979-12-25 Monsanto Company Derivatives of N-trifluoroacetyl-N-phosphonomethylglycinates and the herbicidal use thereof
US4251258A (en) * 1978-09-29 1981-02-17 Monsanto Company N-(Substituted carbonyl) derivatives of N-phosphinylmethylglycinates and the herbicidal use thereof
US4300942A (en) * 1978-09-29 1981-11-17 Monsanto Company N-(Substituted carbonyl) derivatives of N-phos-phinylmethylglycinates and the herbicidal use thereof
US4368162A (en) * 1981-11-02 1983-01-11 Ciba-Geigy Corporation Process for producing aminomethylphosphonic acid
US4389349A (en) * 1982-01-25 1983-06-21 Cho Hung H Process for preparing of N-phosphenomethyl glycine
US4422982A (en) * 1982-06-30 1983-12-27 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
EP0102694A1 (en) * 1982-07-29 1984-03-14 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
EP0149294A1 (en) * 1982-08-16 1985-07-24 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
US4487724A (en) * 1982-08-23 1984-12-11 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
EP0104775A1 (en) * 1982-08-30 1984-04-04 Stauffer Chemical Company Production of N-phosphonomethylglycine
US4415503A (en) * 1982-09-28 1983-11-15 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
US4634788A (en) * 1985-06-06 1987-01-06 Monsanto Company Herbicidal glyphosate oxime derivatives
US5284970A (en) * 1988-11-23 1994-02-08 American Cyanamid Company 2-azabicyclo[2.2.1]hept-5-ene-2-acetic acid, derivatives thereof and related compounds, process for the preparation of said compounds and n-phosphonomethylglycine
EP0374410A2 (en) * 1988-11-23 1990-06-27 American Cyanamid Company 2-Azabicyclo[2.2.1]hept-5-ene-2-acetic acid, derivatives thereof and related compounds, process for the preparation of said compounds and the use of said compounds for the manufacture of N-phosphonomethylglycine
EP0374410A3 (en) * 1988-11-23 1992-06-10 American Cyanamid Company 2-Azabicyclo[2.2.1]hept-5-ene-2-acetic acid, derivatives thereof and related compounds, process for the preparation of said compounds and the use of said compounds for the manufacture of N-phosphonomethylglycine
US5149825A (en) * 1988-11-23 1992-09-22 American Cyanamid Company 2-azabicyclo(2.2.1)hept-5-ene-2-acetic acid, derivatives thereof and related compounds, process for the preparation of said compounds and the use of said compounds for the manufacture of N-phosphonomethylglycine
US5053529A (en) * 1990-05-25 1991-10-01 Korea Institute Of Science And Technology Process for the preparation of N-phosphonomethylglycine
US5294632A (en) * 1991-05-01 1994-03-15 Ciba-Geigy Corporation Phosphono/biaryl substituted dipetide derivatives
US5155100A (en) * 1991-05-01 1992-10-13 Ciba-Geigy Corporation Phosphono/biaryl substituted dipeptide derivatives
US5210277A (en) * 1991-05-16 1993-05-11 American Cyanamid Company N-[pentaalkyl-cyclopentadienyl)methyl]-glycines
US5270473A (en) * 1991-05-16 1993-12-14 American Cyanamid Company N-[(pentaalkyl-cyclopentadienyl)methyl]-glycines, process for the preparation of the compounds and the use thereof in the manufacture of N-phosphonomethylglycine
US5120871A (en) * 1991-05-16 1992-06-09 American Cyanamid Company N-[(pentaalkyl-cyclopentadienyl)methyl]-glycines, process for the preparation of the compounds and the use thereof in the manufacture of N-phosphonomethylglycine
US20030004370A1 (en) * 1999-12-23 2003-01-02 Christian Wulff Method for production of n-phosphonomethylglycine
US20040063996A1 (en) * 1999-12-23 2004-04-01 Christian Wulff Process for the preparation of N-phosphonomethylglycine
US20040092765A1 (en) * 1999-12-23 2004-05-13 Christian Wulff Process for the preparation of N-phosphonomethylglycine
US6818793B2 (en) 1999-12-23 2004-11-16 Basf Aktiengesellschaft Method for production of n-phosphonomethylglycine
US6855841B2 (en) 1999-12-23 2005-02-15 Basf Aktiengesellschaft Process for the preparation of N-phosphonomethylglycine
US20040236145A1 (en) * 2001-06-22 2004-11-25 Christian Wulff Method for producing n-phosphonomethylglycine
US7145034B2 (en) 2001-06-22 2006-12-05 Basf Aktiengesellschaft Method for producing N-phosphonomethylglycine

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GB1527191A (en) 1978-10-04
SU662015A3 (en) 1979-05-05
IT1075476B (en) 1985-04-22
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IE44245L (en) 1977-07-05
ATA277A (en) 1978-07-15
DE2700017A1 (en) 1977-07-14
FR2337143A1 (en) 1977-07-29
IL51203A (en) 1980-05-30
PL105557B1 (en) 1979-10-31
JPS5285122A (en) 1977-07-15
DE2700017C2 (en) 1984-12-06
AU508058B2 (en) 1980-03-06
YU39981B (en) 1985-06-30
HU174617B (en) 1980-02-28
DD129103A5 (en) 1977-12-28
NL183033C (en) 1988-07-01
IE44245B1 (en) 1981-09-23
JPS5619875B2 (en) 1981-05-09
ZA779B (en) 1977-11-30
IL51203A0 (en) 1977-03-31
AR224493A1 (en) 1981-12-15
NL183033B (en) 1988-02-01
AT348544B (en) 1979-02-26
BE850059A (en) 1977-07-04
MX4089E (en) 1981-12-07
AU2102777A (en) 1978-07-13
PL195088A1 (en) 1978-02-27
CS193080B2 (en) 1979-09-17
ES454709A1 (en) 1978-01-01
BR7700009A (en) 1977-09-06
SE7700032L (en) 1977-07-06
RO71661A (en) 1982-09-09
YU320176A (en) 1982-05-31
PH13277A (en) 1980-02-27
DK377A (en) 1977-07-06
FR2337143B1 (en) 1981-11-20
CH623595A5 (en) 1981-06-15
NL7614584A (en) 1977-07-07

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